Polymerized catalyst composition II

ABSTRACT

Copolymerization of Ni(II) phenol imine complexes containing olefinic substituents on aryl groups with styrene in the presence of a radical initiator results in polymerized late transition metal catalysts which can be used for olefin polymerization or oligomerization. These catalysts have high catalyst activity for olefin polymerization or oligomerization.

PRIORITY CLAIM AND RELATED APPLICATIONS

[0001] This application claims priority from U.S. S No. 60/434,913 filedDec. 20, 2002; U.S. S No. 60/435,228 filed Dec. 20, 2002 and U.S. S No.60/435,046 filed Dec. 20, 2002. This application is related to U.S. SNo. 60/421,282 filed Oct. 25, 2002; U.S. S No. 60/421,163 filed Oct. 25,2002; U.S. S No. 60/421,164 filed Oct. 25, 2002; U.S. S No. 60/433,934filed Dec. 17, 2002; U.S. S No. 60/434,082 filed Dec. 17, 2003 and U.S.S No. 60/446,607 filed Feb. 11, 2003.

FIELD OF THE INVENTION

[0002] This invention relates to methods of polymerizing oroligomerizing one or more olefins, optionally with an activator, withone or more polymerized catalyst compounds prepared by polymerizing oneor more free radical polymerizable monomers (such as styrene) with oneor more different “single component” olefin polymerization catalystprecursors containing terminal unsaturation.

BACKGROUND

[0003] U.S. Pat. No. 5,714,425 describes metallocene catalystcompositions having a polymerizable olefinic group. These metallocenesare described as being useful to prepare polyolefins. In addition, thesemetallocenes are described as being polymerized with one or morealpha-olefins so that the metallocene is copolymerized with thealpha-olefin. This composition is then described as useful to polymerizeolefins. But U.S. Pat. No. 5,714,4254 does not disclose free-radicalpolymerization of catalyst compositions having a polymerizable olefinicgroup with monomers such as styrene, isobutylene, 1,3-butadiene and thelike.

[0004] U.S. Pat. No. 5,679,816 discloses biscyclopentadienyltransition-metal complexes containing a conjugated diene ligand group.

[0005] U.S. Pat. No. 6,150,544 and U.S. Pat. No. 6,352,953 disclosebimetallic, metallacyclic catalyst compounds where one metal is aGroup-4 metal and the other metal is a Group-3 metal. (Likewise, it isalso known in the art to prepolymerize a heterogeneous catalyst systemin the presence of at least one olefin see EPA 426,646 and U.S. Pat. No.4,871,705.)

SUMMARY

[0006] This invention relates to a composition comprising the product ofcombining, in the presence of a free radical initiator, one or moremonomers that can be polymerized by a free radical initiator and acatalyst precursor represented by the formula:

[0007] wherein X is a hydrocarbyl group or a halide, Y is a neutralLewis base, and TM is any Group-4-11 metal, any Group-10 metal, or Ni.R¹, R², R³ and R⁴ are independently hydrogen or hydrocarbyl groups. R¹R² R³, R⁴ H H IPr NO₂ NO₂ IPr tBu Me IPr Ph H IPr Ph H Me

[0008] This invention also relates to the above complex copolymerizedwith other molecules provided that the polymerization method isfree-radical initiable. This invention also relates to methods topolymerize olefins using the above compositions. These complexes aloneor when copolymerized with other molecules are sometimes called catalystsystems.

DETAILED DESCRIPTION

[0009] Definitions

[0010] The term “hydrocarbyl radical” is sometimes used interchangeablywith “hydrocarbyl” throughout this document. For purposes of thisdisclosure, “hydrocarbyl radical” encompasses C₁-C₂₀₀ radicals. Theseradicals can be linear, branched, or cyclic, and when cyclic, aromaticor non-aromatic. Thus, the term “hydrocarbyl radical”, in addition tounsubstituted hydrocarbyl radicals, encompasses substituted hydrocarbylradicals, halocarbyl radicals, and substituted halocarbyl radicals, asthese terms are defined below.

[0011] Substituted hydrocarbyl radicals are radicals in which at leastone hydrogen atom has been replaced with a functional group such asNR″₂, OR″, PR″₂, SR″, BR″₂, SiR″₃, GeR″₃ and the like or where at leastone non-hydrocarbon atom or group has been inserted within thehydrocarbyl radical, such as O, S, NR″, PR″, BR″, SiR″₂, GeR″₂, and thelike, where R″ is independently a C₁-C₃₀ hydrocarbyl or halocarbylradical.

[0012] Halocarbyl radicals are radicals in which one or more hydrocarbylhydrogen atoms have been substituted with at least one halogen orhalogen-containing group (e.g. F, Cl, Br, I).

[0013] Substituted halocarbyl radicals are radicals in which at leastone hydrocarbyl hydrogen or halogen atom has been substituted with afunctional group such as NR″₂, OR″, PR″₂, SR″, BR″₂, SiR″₃, GeR″₃ andthe like or where at least one non-carbon atom or group has beeninserted within the halocarbyl radical such as O, S, NR″, PR″, BR″,SiR″₂, GeR″₂, and the like where R″ is independently a C₁-C₃₀hydrocarbyl or halocarbyl radical provided that at least one halogenatom remains on the original halocarbyl radical.

[0014] In some embodiments, a hydrocarbyl radical is independentlyselected from methyl, ethyl, propyl, butyl, pentyl, hexyl, phenyl,heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl,pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl, eicosyl,heneicosyl, docosyl, tricosyl, tetracosyl, pentacosyl, hexacosyl,heptacosyl, octacosyl, nonacosyl, triacontyl, propenyl, butenyl,pentenyl, hexenyl, heptenyl, octenyl, nonenyl, decenyl, undecenyl,dodecenyl, tridecenyl, tetradecenyl, pentadecenyl, hexadecenyl,heptadecenyl, octadecenyl, nonadecenyl, eicosenyl, heneicosenyl,docosenyl, tricosenyl, tetracosenyl, pentacosenyl, hexacosenyl,heptacosenyl, octacosenyl, nonacosenyl, triacontenyl, propynyl, butynyl,pentynyl, hexynyl, heptynyl, octynyl, nonynyl, decynyl, undecynyl,dodecynyl, tridecynyl, tetradecynyl, pentadecynyl, hexadecynyl,heptadecynyl, octadecynyl, nonadecynyl, eicosynyl, heneicosynyl,docosynyl, tricosynyl, tetracosynyl, pentacosynyl, hexacosynyl,heptacosynyl, octacosynyl, nonacosynyl, or triacontynyl isomers. Theradical may then be subjected to the types of substitutions describedabove. Also, terms like “propyl” and “hexyl” encompass all isomers, e.g.propyl means both n-propyl and isopropyl; hexyl includes all six carbonisomers including cyclic isomers.

[0015] Ancillary ligands serve to enforce the geometry around the metalcenter.

[0016] An “abstractable ligand” is a ligand that can be abstracted fromthe metal center by a cocatalyst leaving behind an activated catalyst.

[0017] For purposes of this disclosure oligomers have about 2-75 merunits. A mer is defined as a unit of an oligomer or polymer thatoriginally corresponded to the monomer that was used in thepolymerization reaction. For example, the mer of polyethylene would beethylene.

[0018] In some structures throughout this specification, drawing theligand-metal connection with an arrow, showing that the electrons forthe bond originally came from the ligand, sometimes indicatescoordination. At other times, drawing a solid line, showing the bond'scovalent nature, indicates coordination. One of ordinary skill in theart recognizes that these depictions are interchangable.

[0019] The term “alkyl” or “alkyl radical” refer to branched orunbranched, saturated or unsaturated, acyclic hydrocarbyl radical.Suitable alkyl radicals include, for example, methyl, ethyl, n-propyl,i-propyl, 2-propenyl (or allyl), vinyl, n-butyl, t-butyl, i-butyl (or2-methylpropyl). In particular embodiments, alkyls are C₁₋₂₀₀hydrocarbyls, C₁₋₅₀ hydrocarbyls, or C₁₋₂₀ hydrocarbyls.

[0020] For purposes of this disclosure, “comprise” takes the meaning of“include”. When “include” is used, the disclosure intends the openconstruction of “include”. (The set including A, B, and C contains A, B,and C, but may also contain D, E, F, etc.)

[0021] Description

[0022] The inventive polymerized late transition metal catalystprecursors are prepared by copolymerizing transition metal phenolatocomplexes with an olefin such as styrene in the presence of a radicalinitiator (e.g., AIBN). These olefins are sometimes referred to in thisdocument as catalyst polymerization monomer because they are the monomerthat is used in polymerizing the catalyst. These complexes contain arylgroups that are substituted with polymerizable olefinic substituents.Divinyl benzene is optionally added to the copolymerization reactionmedium to promote cross-linking.

[0023] Before polymerization into a co-polystyrene particle, the latetransition metal catalyst precursors are sometimes simply calledcatalyst precursors. After polymerization, the catalyst precursors aresometimes called polymerized catalyst precursors. These catalystprecursors function in the presence of activators, but they are singlecomponent catalyst. This means that an activator is not necessary. Thesecatalysts can polymerize olefins without using an activator to remove anabstractable ligand. Once active, the “polymerized catalyst precursors”are sometimes called polymerized catalysts.

[0024] Inventive transition metal complexes with olefinicallysubstituted aryl groups are synthesized. Then they are free-radicalcopolymerized with an olefin. The resulting copolymer has units ofpolyolefin interspersed with enchained catalyst molecules (catalystprecursors).

[0025] These enchained complexes (catalyst precursors) function asethylene or α-olefin polymerization or oligomerization catalysts.Ethylene or α-olefin monomers are sometimes referred to in thisdocuments as olefin polymerization monomers because they represent themonomer or monomers that become polyolefins when combined with inventioncatalysts (as opposed to when invention catalyst precursors aresubjected to free-radical initiation or polymerization). As shown in theExample section, aryl substituents other than the olefinic substituentsometimes affect catalyst performance.

[0026] Inventive late transition metal complexes are useful to preparecatalysts for olefin polymerization or oligomerization.

[0027] More than one catalyst precursor may be copolymerized with themonomers in varying ratios.

Catalyst Compounds

[0028] Catalyst compounds useful in this invention include thoserepresented by the formulas:

[0029] wherein X is a hydrocarbyl group or a halogen, particularly ahalogen, particularly chlorine; Y is a neutral Lewis base, particularlytriphenyl phosphine or acetonitrile; and M is any Group-4-11 metal,Group-10 metal, or Ni.

[0030] The above picture represents a schematic formula of thepolymerized catalyst after polymerization. The P-labeled circlesrepresent the bulk polyolefin/catalyst copolymer. The C-labeled circlesrepresent the catalyst.

[0031] This section provides examples of how the ligands and complexes,as they exist before free-radical-initiated polymerization, are namedand how the naming convention arises.

[0032] The ligand pictured above is called2-(2,6-diisopropyl-4-allylphenyliminomethyl)-4-tert-butyl-6-methyl-phenol.As is readily apparent, the ligand can be conceptualized as atrisubstituted phenol molecule. In this case, the phenol is substitutedat the 4-position with a tertiary butyl radical. It is also substitutedat the 6-position with a methyl radical. And the phenol ring 2-positionis substituted with a substituted iminomethyl group. The substitution onthe iminomethyl group is bracketed in the picture. This bracketed moeityis a substituted phenyl radical with isopropyl substitutions at its 2and 6 positions and an allyl substitution at its 4-position.

[0033] The ligand pictured above is called2-(2-isopropyl-4-allyl-6-sec-pentylphenyliminomethyl)-4-methyl-6-phenyl-phenol.This ligand can also be conceptualized as a trisubstituted phenolmolecule. In this case, the phenol is substituted at the 4-position witha methyl radical and substituted at the 6-position with a phenylradical. As before, the phenol-ring 2-position is substituted with asubstituted iminomethyl group. Once again, this iminomethyl group isbracketed in the picture. This bracketed moiety is a substituted phenylradical with an isopropyl substitution at its 2-position, a secondarypentyl substitution at its 6-position, and an allyl substitution at its4-position.

[0034] When these types of ligands are ionized by removing hydrogen fromthe phenol OH group, the ligands become bidentate, and can coordinate toan acceptor through the oxygen atom, the nitrogen atom, or both. Forinvention catalysts the acceptor is a transition metal. To indicate thatthe substituted phenol ligand is now acting as a radical, the phenolname receives a suffix, -ate, yielding phenolate. To indicate that thesubstituted phenol ligand is chelating, the phenolate name receives asuffix, -o, yielding phenolato. The ligand pictured below is shownionized. It is called2-(2-isopropyl-4-allyl-6-methylphenyliminomethyl)-4,6-diphenyl-phenolate.

[0035] When the ligand above chelates or coordinates to a transitionmetal such as Ni, the complete name for the complex is2-(2-isopropyl-4-allyl-6-methylphenyliminomethyl)-4,6-diphenyl-phenolatophenyl triphenylphosphine nickel (II). Note that the transition metalhas a charged phenyl ligand and a neutral triphenylphosphine ligand(neutral Lewis base); one or both of these act as the abstractactableligand or leaving group. Thus, during olefin polymerization reactionswith these complexes, either as shown or after their copolymerizationwith a styrenic monomer, the neutral Lewis base is believed todissociate leaving behind a catalyst active for those reactions.

[0036] Useful Catalyst Compounds Include:

[0037] 2-(2,6-dimethyl-4-allyl-phenyliminomethyl)-6-propylphenolatophenyl trimethylamine nickel (II);2-(2,6-dioctyl-4-allyl-phenyliminomethyl)-4-hexyl-6-butylphenolatomethyl dimethyethylamine nickel (II);2-(2,6-diphenyl-4-allyl-phenyliminomethyl)-4-phenyl-6-propylphenolatophenyl trimethylphosphine nickel (II);2-(2,6-diheptadecyl-4-allyl-phenyliminomethyl)-4-propyl-6-ethylphenolatoethyl triethylphosphine nickel (II);2-(2,6-dimethyl-4-allyl-phenyliminomethyl)-6-phenylphenolato ethyltrimethylamine nickel (II);2-(2,6-dioctyl-4-allyl-phenyliminomethyl)-4-tridecyl-6-hexylphenolatophenyl triethylamine nickel (II);2-(2,6-diphenyl-4-allyl-phenyliminomethyl)-4-octylphenolato hydridotriethylphosphine nickel (II);2-(2,6-diphenyl-4-allyl-phenyliminomethyl)-4,6-dimethylphenolato hydridotriethylphosphine nickel (II);2-(2,6-dimethyl-4-allyl-phenyliminomethyl)-4-octyl-6-phenylphenolatophenyl trimethylphosphine nickel (II);2-(2,6-dioctyl-4-allyl-phenyliminomethyl)-6-ethylphenolato methyltrimethylphosphine nickel (II);2-(2,6-dioctyl-4-allyl-phenyliminomethyl)-4-octyl-6-hexylphenolatophenyl triethylamine nickel (II);2-(2,6-dimethyl-4-allyl-phenyliminomethyl)-4-propyl-6-octylphenolatohydrido triethylamine nickel (II);2-(2,6-diphenyl-4-allyl-phenyliminomethyl)-4-phenyl-6-tetradecylphenolatoethyl trimethylphosphine nickel (II);2-(2,6-dioctyl-4-allyl-phenyliminomethyl)-4-ethylphenolato phenyltriphenylphosphine nickel (II);2-(2,6-dimethyl-4-allyl-phenyliminomethyl)-4,6-diphenylphenolato hydridotriethylamine nickel (II);2-(2,6-diphenyl-4-allyl-phenyliminomethyl)-4-octyl-6-phenylphenolatophenyl triphenylphosphine nickel (II);2-(2,6-dioctadecyl-4-allyl-phenyliminomethyl)-4-phenyl-6-ethylphenolatoethyl trimethylphosphine nickel (II);2-(2,6-dipropyl-4-allyl-phenyliminomethyl)-4,6-dioctylphenolato methyltriethylphosphine nickel (II);2-(2,6-diphenyl-4-allyl-phenyliminomethyl)phenolato iodo trimethylaminenickel (II);2-(2,6-dimethyl-4-allyl-phenyliminomethyl)-4-phenyl-6-hexylphenolatohydrido trimethylamine nickel (II);2-(2,6-dimethyl-4-allyl-phenyliminomethyl)-4-hexyl-6-methylphenolatohydrido triethylphosphine nickel (II);2-(2,6-diethyl-4-allyl-phenyliminomethyl)-6-phenylphenolato hydridotrimethylamine nickel (II);2-(2,6-diethyl-4-allyl-phenyliminomethyl)-4-phenyl-6-ethylphenolatohydrido methydiethylphosphine nickel (II);2-(2,6-diethyl-4-allyl-phenyliminomethyl)-6-octylphenolato iodotrimethylamine nickel (II);2-(2,6-dimethyl-4-allyl-phenyliminomethyl)-4,6-dimethylphenolato hydridotriphenylphosphine nickel (II);2-(2,6-ditetradecyl-4-allyl-phenyliminomethyl)-4-hexyl-6-propylphenolatohydrido triphenylphosphine nickel (II);2-(2,6-dioctyl-4-allyl-phenyliminomethyl)-4-phenyl-6-tetradecylphenolatophenyl triphenylphosphine nickel (II);2-(2,6-dipropyl-4-allyl-phenyliminomethyl)-4-octadecyl-6-propylphenolatophenyl trimethylphosphine nickel (II);2-(2,6-dioctyl-4-allyl-phenyliminomethyl)-6-ethylphenolato ethyltriethylphosphine nickel (II);2-(2,6-diphenyl-4-allyl-phenyliminomethyl)-6-tetradecylphenolato hydridomethydiethylphosphine nickel (II);2-(2,6-dioctyl-4-allyl-phenyliminomethyl)-4,6-diphenylphenolato methyltrimethylphosphine nickel (II);2-(2,6-dipentyl-4-allyl-phenyliminomethyl)-6-nonadecylphenolato hydridotriethylamine nickel (II);2-(2,6-dipropyl-4-allyl-phenyliminomethyl)-4-ethyl-6-propylphenolatophenyl dimethyethylamine nickel (II);2-(2,6-diethyl-4-allyl-phenyliminomethyl)-6-phenylphenolato methyltriethylamine nickel (II);2-(2,6-dimethyl-4-allyl-phenyliminomethyl)-6-hexylphenolato phenyldimethyethylamine nickel (II);2-(2,6-diphenyl-4-allyl-phenyliminomethyl)-4-octyl-6-ethylphenolatophenyl triethylamine nickel (II);2-(2,6-dioctadecyl-4-allyl-phenyliminomethyl)-4-propyl-6-phenylphenolatooctyl triphenylamine nickel (II);2-(2,6-diodadecyl-4-allyl-phenyliminomethyl)-4-hexyl-6-ethylphenolatoethyl triethylphosphine nickel (II);2-(2,6-diethyl-4-allyl-phenyliminomethyl)-4-nonyl-6-nonadecylphenolatophenyl triphenylphosphine nickel (II);2-(2,6-diphenyl-4-allyl-phenyliminomethyl)-4-phenylphenolato methyltriethylphosphine nickel (II);2-(2,6-diphenyl-4-allyl-phenyliminomethyl)-4-ethylphenolato methylmethydiethylphosphine nickel (II);2-(2,6-diethyl-4-allyl-phenyliminomethyl)-6-phenylphenolato phenyltriphenylphosphine nickel (II);2-(2,6-dihexyl-4-allyl-phenyliminomethyl)-4-methylphenolato hydridotriphenylamine nickel (II);2-(2,6-diethyl-4-allyl-phenyliminomethyl)-4-octyl-6-phenylphenolatomethyl triethylamine nickel (II);2-(2,6-dioctyl-4-allyl-phenyliminomethyl)-4-octyl-6-phenylphenolatohydrido trimethylamine nickel (II);2-(2,6-dioctyl-4-allyl-phenyliminomethyl)-4-octyl-6-phenylphenolatophenyl methydiethylphosphine nickel (II);2-(2,6-dimethyl-4-allyl-phenyliminomethyl-4-phenyl-6-hexylphenolatophenyl triphenylphosphine nickel (II);2-(2,6-dimethyl-4-allyl-phenyliminomethyl-4-ethyl-6-octadecylphenolatophenyl triphenylphosphine nickel (II);2-(2,6-diphenyl-4-allyl-phenyliminomethyl-4-octyl-6-phenylphenolatophenyl trimethylphosphine nickel (II);2-(2,6-dihexyl-4-allyl-phenyliminomethylphenolato phenyltrimethylphosphine nickel (II);2-(2,6-diethyl-4-allyl-phenyliminomethyl-4-dodecyl-6-hexylphenolatohydrido triethylamine nickel (II);2-(2,6-dimethyl-4-allyl-phenyliminomethyl-4-phenylphenolato methyltrimethylphosphine nickel (II);2-(2,6-diphenyl-4-allyl-phenyliminomethyl-6-methylphenolato hydridotrimethylphosphine nickel (II);2-(2,6-diphenyl-4-allyl-phenyliminomethyl-4-nonyl-6-phenylphenolatoethyl trimethylamine nickel (II);2-(2,6-diphenyl-4-allyl-phenyliminomethyl-4,6-dihexylphenolato hydridotrimethylamine nickel (II);2-(2,6-dinonyl-4-allyl-phenyliminomethyl-4,6-dihexylphenolato hydridotriphenyphosphine nickel (II);2-(2,6-diphenyl-4-allyl-phenyliminomethyl-4,6-dioctylphenolato phenyltriethylphosphine nickel (II);2-(2,6-dihexyl-4-allyl-phenyliminomethyl-4,6-diphenylphenolato hydridotrimethylamine nickel (II);2-(2,6-dipentadecyl-4-allyl-phenyliminomethyl-4,6-diundecylphenolatobutyl trimethylamine nickel (II);2-(2,6-dipropyl-4-allyl-phenyliminomethyl-4,6-dimethylphenolato phenyltriethylamine nickel (II);2-(2,6-dioctyl-4-allyl-phenyliminomethyl-4,6-diphenylphenolato iododimethyethylamine nickel (II);2-(2,6-dioctyl-4-allyl-phenyliminomethyl-4,6-dihexylphenolato phenylmethydiethylphosphine nickel (II);2-(2,6-dimethyl-4-allyl-phenyliminomethyl-4,6-diethylphenolato phenyltriethylphosphine nickel (II);2-(2,6-dimethyl-4-allyl-phenyliminomethylphenolato hydridodimethyethylamine nickel (II);2-(2,6-dipentadecyl-4-allyl-phenyliminomethyl-4,6-dihexylphenolato butyltriethylphosphine nickel (II);2-(2,6-dioctyl-4-allyl-phenyliminomethyl-4,6-diphenylphenolato ethylmethydiethylphosphine nickel (II);2-(2,6-dihexyl-4-allyl-phenyliminomethylphenolato hydridodimethyethylamine nickel (II);2-(2,6-dipropyl-4-allyl-phenyliminomethyl-4,6-dipropylphenolato phenyltriphenylphosphine nickel (II).

[0038] The catalyst compounds described above may be prepared accordingto Scheme I:

[0039] The first step in preparing invention catalysts is to prepare theancillary ligand. The ancillary ligand can be thought of as asubstituted phenol. In Scheme I the phenol substituents are generic R¹and R² and a substituted methyl radical that is substituted itself. Themethyl radical is substituted with an imino group; the imino group isalso substituted; substituted with a substituted phenyl group. When R³and R⁴ are isopropyl, R² is hydrogen, and R¹ is phenyl, the ancillaryligand precursor shown in Scheme I (Ligand I) is called2-(2,6-diisopropyl-4-allyl-phenyliminomethyl)-6-phenylphenol.

[0040] Synthesis of the ligand can occur through coupling its two mainportions, the aniline and the aldehyde, such that an iminomethylconnection occurs. One way of accomplishing this is shown in Scheme I.The coupling reaction is the acid-catalyzed addition of an aniline tothe benzaldehyde carbonyl group (with the loss of water).

[0041] Once the two main ligand portions are connected, synthesis of theancillary ligand is complete. After this, the ligand is reduced and thensimply complexed with an appropriate transition metal halide by mixingthe halide and the ligand together. The overall name of the catalystcomplex before it is copolymerized with an olefinic monomer is2-(2,6-diisopropyl-4-allyl-phenyliminomethyl)-6-phenylphenolato phenyltriphenylphosphine nickel (II). Those of ordinary skill in the art willrecognize that other synthetic pathways exist for making these ligands

[0042] Process to Prepare the Polymerized Catalyst Compounds

[0043] The catalyst precursor described above is then contacted with afree radical initiator and one or more monomers that can be polymerizedby a free radical initiator. This yields a copolymer containing thephenolato-based olefin polymerization catalyst precursor.

[0044] A typical transition metal catalyst can be polymerized using thefollowing procedure. 50 ml of a toluene solution with theterminal-unsaturation-containing catalyst, styrene, and AIBN aremaintained at 80° C. for 7 hrs. The resulting solution is evaporated andthe residue is washed with a mixture of hexane and toluene (2:1) anddried. Then, the solid polymer product is collected. Analogous methodsyield the other disclosed polymerized catalysts.

[0045] The polymerization typically takes place in solution at atemperature of 30-100° C., 50-90° C., 70-85° C., or 75-85° C. Suitablesolvents include toluene, benzene, xylene, and hexane. Desired solventsare selected from those that can dissolve theterminal-unsaturation-containing catalyst.

[0046] The polymerization may be performed at atmospheric,sub-atmospheric or super-atmospheric pressures.

[0047] Generally, the structure of a catalyst will look like this beforecopolymerization.

[0048] Scheme II illustrates the catalyst polymerization.

[0049] The polymerized catalyst compounds typically have Mw of up to300,000; 500-150,000; 1,000-100,000; 5,000-75,000; or 10,000-50,000.

Free Radical Initiators

[0050] Free radical initiators that are useful in this inventioninclude: (1) thermally decomposable compounds that generate radicalssuch as azo compounds or organic peroxides; (2) compounds that generatefree radicals by non-thermal methods such as photochemical or redoxprocesses; (3) compounds that have inherent radical character such asmolecular oxygen; or (4) electromagnetic radiation such as X-rays,electron beams, visible light and ultraviolet-light. Suitable organicperoxide compounds include hydroperoxides, dialkyl peroxides, diacylperoxides, peroxyesters, peroxydicarbonates, peroxyketals, ketoneperoxides and organosulfonyl peroxides. Especially preferred peroxidesare t-butyl perbenzoate, dicumyl peroxide,2,5-dimethyl-2,5-di-tert-butylperoxy-3-hexyne (Lupersol 130),α,α-bis(tert-butylperoxy)diisopropyl benzene (VulCup R).

[0051] Any free radical initiator or mixture having a 10-hour half-lifetemperature over 80° C. or their mixtures may function as the initiatorin invention processes to prepare supported polymerized catalystcompounds. Generally, the higher the decomposition temperature of theperoxygen compound the better. See pages 66-67 of Modern Plastics,November 1971 for a more complete list of these compounds.

[0052] In one embodiment, the free radical initiator is an organicperoxide compound having a half-life, at the reaction temperature, ofless than one tenth of the reaction/residence time employed. The freeradical initiator is used at concentrations of 1-5% weight percent basedon styrene (or other mononmer).

[0053] The following classes and examples of free-radical initiators areuseful in polymerizing invention terminal-unsaturation-containingcatalyst precursors. Azo initiators Dialkyldiazenes 2,2′-azobis(2-methylpropanenitrile) (AIBN) 1,1-azobis(1- cyclohexanenitrile)4,4′-azobis(4-cyanovaleric acid) riphenylmethylazobenzene Hyponitritesdi-t-butyl hyponitrite Dicumyl hyponitrite Peroxides diacyl peroxidesDibenzoyl peroxide Didodecanoyl peroxide Diacetyl peroxide Dialkylperoxydicarbonates Diisopropyl ester Dicyclohexyl ester Peresters alkylhydroperoxides Cumyl hydroperoxide t-butyl hydroperoxide dialkylperoxides Dicumyl peroxide di-t-butyl peroxide inorganic peroxidesHydrogen peroxide persulfate

Monomers Polymerizable by a Free Radical Initiator

[0054] Monomers that can be polymerized by a free radical processinclude ethylene, 1,3-butadiene, isoprene, styrene, alkyl styrene,isobutylene, vinyl chloride, vinylidene chloride, vinyl fluoride,tetrafluoroethylene, vinyl esters, acrylic esters, methacrylic esters,acrylonitrile, and propylene. Therefore, any of these can becopolymerized with the catalyst compound containing the terminalunsaturation. For example, selecting isoprene for copolymerizationresults in a catalyst/isoprene copolymer.

Process to Polymerize Olefins Using Polymerized Catalyst Compounds

[0055] Some of the catalyst systems described above are suitable for usein solution polymerization processes, some for use in gas-phaseprocesses, and some in slurry processes. Some of the catalyst systemsabove are suitable for use in combinations of those processes.

[0056] In invention polymerization or oligomerization processes usinginvention catalyst systems, the process temperature can be −100° C. to300° C., −20° C. to 200° C., or 0° C. to 150° C. Given one of thesetemperature ranges, the following ethylene oligomerization pressures(gauge) are useful: 0 kPa-35000 kPa or 500 kPa-15000 kPa.

[0057] In polymerization or oligomerization processes using inventioncatalyst systems and any of the process conditions described above,whether the selected process is solution, slurry, gas-phase or anamalgamation of these, the process can employ one or more, C₂-C₃₀monomers. Alternatively, C₂-C₁₂ or C₂-C₈ monomers are suitable. Specificexamples of invention-suitable monomers include one or more of ethylene,propylene, butene-1, pentene-1,4-methyl-pentene-1, hexene-1, octene-1,decene-1,3-methyl-pentene-1, and cyclic olefins, or their combinations.Other monomers can include vinyl monomers, diolefins such as dienes,polyenes, norbornene, norbornadiene, vinyl norbornene, ethylidenenorbornene monomers. Alternatively, invention polymerization processesproduce homopolymers or copolymers of ethylene or propylene.

[0058] In polymerization or oligomerization processes using inventioncatalyst systems and any of the process conditions described above,polymerization with ethylene and at least two different comonomers formsterpolymers. Invention comonomers comprise a combination of any of themonomers described above or of C₂-C₃₀ or C₄-C₈, α-olefin monomers,optionally with at least one diene monomer. Terpolymers includecombinations such as propylene/but-1-ene/hex-1-ene,propylene/but-1-ene/ethylene, propylene/ethylene/hex-lene,propylene/butene/norbornene, propylene/butene/decadiene, and the like.For purposes of this disclosure, nomenclature such as “but-1-ene”, whichindicates that the olefinic unsaturation in the butene molecule beginsat the first atom in the butene carbon chain, is equivalent to“butene-1”.

[0059] Invention oligomerization or polymerization processes can be runin the presence of various liquids, particularly aprotic organicliquids. In some embodiments the catalyst system is insoluble in mostsolvents; and thus, the polymerization will be slurry phase rather thansolution phase. Liquid-suitable invention catalyst systems includealkanes, alkenes, cycloalkanes, selected halogenated hydrocarbons,aromatic hydrocarbons, and in some cases, hydrofluorocarbons as thesolvent. Useful solvents specifically include hexane, toluene,cyclohexane, and benzene.

Gas-Phase polymerization

[0060] In polymerization or oligomerization processes using inventioncatalyst systems, the reactor pressure in a gas-phase process can varyfrom 69-3500 kPa, alternatively from 690 kPa-3500 kPa, from 1379kPa-2800 kPa, or from 1700-2414 kPa. Invention processes and catalystsystems can use suitable gas-phase polymerization processes; some ofthese processes are described below.

[0061] In gas-phase polymerization or oligomerization processes usinginvention catalyst systems, given a particular reactor pressure range,the reactor temperature can vary from 30-120° C., alternatively from60-115° C., from 70-110° C., or from 70-95° C. The reactor temperatureis typically between 70-105° C. for high-density polyethylene.

[0062] In gas-phase polymerization or oligomerization processes usinginvention catalyst systems, monomer partial pressure influences catalystsystem productivity. Primary monomer concentration, such as ethylene orpropylene, is from 25-90 mole percent, and its partial pressure is from138-517 kPa or 517-2100 kPa. These conditions suit invention gas-phasepolymerization or oligomerization processes. Also, in some systems,comonomer increases productivity.

[0063] Gas-phase polymerization or oligomerization processes usinginvention catalyst systems can produce 227-90,900 kg/hr of polymer,alternatively, 227-455 kg/hr, 227-4540 kg/hr, 227-11,300 kg/hr,227-15,900 kg/hr, 227-22,700 kg/hr, and alternatively 29,000kg/hr-45,500 kg/hr, or 45,500 kg/hr or more.

[0064] Gas-phase polymerization or oligomerization processes usinginvention catalyst systems can use the processes described in U.S. Pat.Nos. 5,627,242, 5,665,818 and 5,677,375, and European publicationsEP-A-0 794 200, EP-A-0 802 202 and EP-B-634 421.

[0065] In some gas-phase polymerization or oligomerization processesusing invention catalyst systems, the reactor receives the liquid orsolution catalyst system in its liquid form at a resin-particle-leanzone. For information on how to introduce a liquid catalyst system intoa fluidized bed polymerization reactor at a resin-particle-lean zone,see U.S. Pat. No. 5,693,727.

[0066] Gas-phase polymerization or oligomerization processes usinginvention catalyst systems can operate with scavengers. Typicalscavengers include trimethyl aluminum, tri-isobutyl aluminum, an excessof alumoxane or modified alumoxane, triethylaluminum,tri-n-hexylaluminum, diethyl aluminum chloride, dibutyl zinc and thelike. PCT publication WO 96/08520 and U.S. Pat. No. 5,712,352 describeprocesses using these scavengers. Invention, gas-phase processes orcatalyst systems can use these processes. Alternatively, gas-phasepolymerization or oligomerization processes using invention catalystsystems can operate in the absence of or essentially free of scavengers.

Slurry Polymerization

[0067] In polymerization or oligomerization processes using inventioncatalyst systems, slurry polymerization processes generally usepressures of 103-5068 kPa guage and temperatures of 0-120° C. Inventionprocesses and catalyst systems can use suitable slurry polymerizationprocesses; some of these processes are described below.

[0068] Typically, in a slurry polymerization, a suspension of solid,particulate polymer forms in a liquid polymerization medium to whichethylene (or α-olefinic monomer), (optional) comonomer, and catalyst,has been added. This suspension intermittently or continuouslydischarges from the reactor, after which the process separates thepolymer from the volatile components and recycles them to the reactor(optionally after a distillation). The liquid employed in thepolymerization medium typically comprises a C₃-C₇ alkane, alternativelya branched alkane. The medium should be liquid and relatively inertunder the polymerization conditions. For propane media, processtemperatures and pressures are usually above the media's criticaltemperature and pressure. The processes can use hexane or isobutanemedia, as well.

[0069] One slurry polymerization process is a particle-formpolymerization. It is a process where the temperature remains below thetemperature at which the polymer appreciably dissolves in the reactionmedium. Such techniques are well known in the art. U.S. Pat. No.3,248,179. Particle-form process temperatures range from 85° C.-110° C.Two other slurry polymerization varieties employ a loop reactor or aplurality of stirred reactors in series, parallel, or combinationsthereof. These reactors can have cooling or not and can employrefrigerated or unrefrigerated monomer feeds. Non-limiting examples ofslurry processes include continuous-loop and stirred-tank processes.Also, U.S. Pat. No. 4,613,484 describes other examples of slurryprocesses.

[0070] Slurry processes can use a continuous-loop reactor. The processregularly injects the catalyst, as a slurry in a compatible solvent oras a dry, free-flowing powder, into the reactor loop. The loop containsa circulating slurry of growing polymer particles in a diluent ofisobutane containing monomer and comonomer. If desired, this process cancontrol molecular weight with hydrogen. The reactor is maintained at apressure of 3.620-4.309 MPa and at a temperature of 60-104° C. dependingon the desired polymer density. Reaction heat is removed from thereactor through the loop wall since much of the reactor vessel is adouble-jacketed pipe. The slurry discharges from the reactor at regularintervals or continuously. It discharges into a heated, low-pressureflash vessel, rotary dryer, and nitrogen purge column, in sequence, toremove isobutane diluent and all unreacted monomer and comonomer. Theresulting hydrocarbon-free powder is then compounded for use in variousapplications.

[0071] Polymerization or oligomerization processes using inventioncatalyst systems and using slurry polymerization conditions can produce1-100,000 kg polymer/hr, 907-100,000 kg/hr, 2268-100,000 kg/hr,4540-100,000 kg/hr, 6804-100,000 kg/hr, 11,340-100,000 kg/hr, or45,500-100,000 kg/hr.

[0072] Polymerization or oligomerization processes using inventioncatalyst systems and using slurry polymerization conditions can usetotal reactor pressures in the range of 2758-5516 kPa, 3103-4827 kPa,3448-4482 kPa, or 3620-4309 kPa.

[0073] Polymerization or oligomerization processes using inventioncatalyst systems and using slurry polymerization conditions can useconcentrations of predominant monomer in the reactor liquid medium of1-10 wt %, 2-7 wt %, 2.5-6 wt %, or 3-6 wt %.

[0074] As with gas-phase polymerization conditions, polymerization oroligomerization processes using invention catalyst systems and slurrypolymerization conditions can use slurry process variants that includeor exclude scavengers.

Applications of Invention Polyolefins

[0075] Invention processes prepare homo- and co-polymer polyethyleneuseful for formulating adhesives and other materials. The termsinvention polymers or invention copolymers refer to polymers made withinvention catalysts or catalyst systems.

Formulations

[0076] In some embodiments, the polymer produced by this invention maybe blended with one or more other polymers such as thermoplasticpolymer(s) and elastomer(s).

[0077] A thermoplastic polymer is a polymer that can be melted byheating and then cooled without appreciable change in properties.Thermoplastic polymers typically include polyolefins, polyamides,polyesters, polycarbonates, polysulfones, polyacetals, polylactones,acrylonitrile-butadiene-styrene resins, polyphenylene oxide,polyphenylene sulfide, styrene-acrylonitrile resins, styrene maleicanhydride, polyimides, aromatic polyketones, or mixtures of two or moreof the above. Specific polyolefins include polymers comprising one ormore, linear, branched, or cyclic, C₂-C₄₀ olefins, preferably polymerscomprising ethylene or propylene copolymerized with one or more, C₃-C₄₀olefins, C₃-C₂₀ α-olefins, or C₃-C₁₀ α-olefins.

[0078] Elastomers include all natural and synthetic rubbers, includingthose defined in ASTM D1566. Examples of elastomers include ethylenepropylene rubber, ethylene propylene diene monomer rubber, styrenicblock copolymer rubbers (including SI, SIS, SB, SBS, SIBS and the like,where S=styrene, I=isobutylene, and B=butadiene), butyl rubber,halobutyl rubber, copolymers of isobutylene and para-alkylstyrene,halogenated copolymers of isobutylene and para-alkylstyrene, naturalrubber, polyisoprene, copolymers of butadiene with acrylonitrile,polychloroprene, alkyl acrylate rubber, chlorinated isoprene rubber,acrylonitrile chlorinated isoprene rubber, polybutadiene rubber (bothcis and trans).

[0079] In another embodiment polymer produced by this invention iscombined with one or more isotactic polypropylenes; highly isotacticpolypropylenes; syndiotactic polypropylenes; random copolymers ofpropylene and ethylene or butene or hexene; polybutenes; ethylene vinylacetate; low-density polyethylenes (density 0.915 to 0.935 g/cm³);linear-low-density polyethylenes; ultra-low-density polyethylenes(density 0.86 to 0.90 g/cm³); very-low-density polyethylenes (density0.90 to 0.915 g/cm³); medium-density polyethylenes (density 0.935 to0.945 g/cm³); high-density polyethylenes (density 0.945 to 0.98 g/cm³);ethylene vinyl acetates; ethylene methyl acrylates; copolymers ofacrylic acid, polymethylmethacrylate, or any other polymerspolymerizable by high-pressure free radical processes;polyvinylchlorides, polybut-1-enes; isotactic polybutenes; ABS resins;ethylene-propylene rubbers (EPR); vulcanized EPRs; EPDMs; blockcopolymers; styrenic block copolymers; polyamides; polycarbonates; PETresins; crosslinked polyethylenes; copolymers of ethylene and vinylalcohol (EVOH); or polymers of aromatic monomers such as polystyrene;poly-1-esters; polyacetal; polyvinylidine fluoride; polyethyleneglycols; or polyisobutylenes.

[0080] In another embodiment, elastomers are blended with the polymerproduced by this invention to form rubber-toughened compositions. Insome embodiments, the rubber toughened composition is a two (or more)phase system where the elastomer is a discontinuous phase and thepolymer produced by this invention is a continuous phase. This blend maybe combined with tackifiers or other additives as is known in the art.

[0081] In another embodiment, the polymer produced by this invention maybe blended to form impact copolymers. In some embodiments, the blend isa two (or more) phase system with a discontinuous phase and a continuousphase. This blend may be combined with tackifiers or other additives asis known in the art.

[0082] In some embodiments invention polymers are combined withmetallocene polyethylenes (mPEs) or metallocene polypropylenes (mPPs).The mPE and mPP homopolymers or copolymers are typically produced usingmono- or bis-cyclopentadienyl transition metal catalysts in combinationwith alumoxane or a non-coordinating anion activator in solution,slurry, high-pressure, or gas-phase conditions. The supported orunsupported catalyst and activator may have substituted or unsubstitutedcyclopentadienyl rings. ExxonMobil Chemical Company (Baytown, Tex.)produces several commercial products with such catalyst and activatorcombinations. These are commercially available under the tradenamesEXCEED™, ACHIEVE™, and EXACT™. For more information on the methods andcatalyst-activator pairs used to produce such homopolymers andcopolymers, see WO 94/26816; WO 94/03506; EPA 277,003; EPA 277,004; U.S.Pat. No. 5,153,157; U.S. Pat. No. 5,198,401; U.S. Pat. No. 5,240,894;U.S. Pat. No. 5,017,714; CA 1,268,753; U.S. Pat. No. 5,324,800; EPA129,368; U.S. Pat. No. 5,264,405; EPA 520,732; WO 92 00333; U.S. Pat.No. 5,096,867; U.S. Pat. No. 5,507,475; EPA 426 637; EPA 573 403; EPA520 732; EPA 495 375; EPA 500 944; EPA 570 982; WO91/09882; WO94/03506and U.S. Pat. No. 5,055,438.

[0083] In some embodiments invention polymers are present in the aboveblends, at from 10-99 wt %, 20-95 wt %, 30-90 wt %, 40-90 wt %, 50-90 wt%, 60-90 wt %, 70-90 wt %. (Based upon the weight of the polymers in theblend.)

[0084] The blends described above may be produced by mixing theinvention polymers with one or more polymers (as described above), byconnecting reactors together in series to make reactor blends, or byusing more than one catalyst in the same reactor to produce multiplespecies of polymer. The polymers can be mixed together before being putinto the extruder or may be mixed in the extruder.

[0085] Any of the above polymers may be functionalized, which means thatthe polymer has been reacted with an unsaturated acid or anhydride.Unsaturated acids and anhydrides include any unsaturated organiccompound containing at least one double bond and at least one carbonylgroup. Representative acids include carboxylic acids, anhydrides, estersand their metallic and non-metallic salts. In some embodiments theorganic compound contains an ethylenic unsaturation conjugated with acarbonyl group (—C═O). Examples include maleic, fumaric, acrylic,methacrylic, itaconic, crotonic, alpha.methyl crotonic, and cinematicacids as well as their anhydrides, esters and salt derivatives. Theunsaturated acid or anhydride is present at 0.1-10 wt %, 0.5-7 wt % or1-4 wt %, based upon the weight of the hydrocarbon resin and theunsaturated acid or anhydride.

[0086] Tackifiers may be blended with invention polymers or with blendsof invention polymers (as described above). Examples of usefultackifiers include aliphatic hydrocarbon resins, aromatic modifiedaliphatic hydrocarbon resins, hydrogenated polycyclopentadiene resins,polycyclopentadiene resins, gum rosins, gum rosin esters, wood rosins,wood rosin esters, tall oil rosins, tall oil rosin esters, polyterpenes,aromatic modified polyterpenes, terpene phenolics, aromatic modifiedhydrogenated polycyclopentadiene resins, hydrogenated aliphatic resin,hydrogenated aliphatic aromatic resins, hydrogenated terpenes andmodified terpenes, and hydrogenated rosin esters. In some embodiments,the tackifier is hydrogenated. In other embodiments, the tackifier isnon-polar. (Non-polar means that the tackifier is substantially free ofmonomers having polar groups. Some tackifier compositions limit thepolar-group content to 5 wt % or less, alternatively, 2 or 0.5 wt % orless.) In some embodiments the tackifier has a softening point (Ring andBall, as measured by ASTM E-28) of 80-40 or 100-30° C. In someembodiments, the tackifier is functionalized, which means that thehydrocarbon resin has been contacted with an unsaturated acid oranhydride. Some embodiments select unsaturated acids or anhydrides fromany unsaturated organic compound containing at least one double bond andat least one carbonyl group. Representative acids include carboxylicacids, anhydrides, esters and their salts, both metallic andnon-metallic. In some embodiments the organic compound contains anethylenic unsaturation conjugated with a carbonyl group (—C═O). Examplesinclude maleic, fumaric, acrylic, methacrylic, itaconic, crotonic,alpha.methyl crotonic, and cinnamic acids as well as their anhydrides,esters and salt derivatives. The unsaturated acid or anhydride ispresent at 0.1 wt %, alternatively 0.5 wt % or 1 wt %, based upon theweight of the hydrocarbon resin and the unsaturated acid or anhydride.

[0087] Invention polymers, or their blends, may further comprise acrosslinking agent. Particularly suitable crosslinking agents includethose having functional groups that can react with the acid or anhydridegroup. Alcohols, multiols, amines, diamines, and triamines belong to anonexclusive list of crosslinking agents. Examples of usefulcrosslinking agents include polyamines such as ethylenediamine,diethylenetriamine, hexamethylenediamine, diethylaminopropylamine, andmenthanediamine.

[0088] Invention polymers, or their blends, may further comprise typicaladditives known in the art such as fillers, cavitating agents,antioxidants, surfactants, adjuvants, plasticizers, antiblock additives,color masterbatches, pigments, dyes, processing aids, UV stabilizers,neutralizers, lubricants, waxes, or nucleating agents. Typically, theseadditives are present in amounts well known to be effective in the art:such as 0.001-10 wt %.

[0089] Specific fillers, cavitating agents, or nucleating agents includetitanium dioxide, calcium carbonate, barium sulfate, silica, silicondioxide, carbon black, sand, glass beads, mineral aggregates, talc,clay, etc.

[0090] Effective antioxidants include phenolic antioxidants, such asIrganox 1010, Irganox, 1076 both available from Ciba-Geigy. Effectiveoils include paraffinic or naphthenic oils, such as Primol 352 or Primol876 available from ExxonMobil Chemical France, S.A. (Paris, France) andaliphatic naphthenic oils, white oils, etc.

[0091] Effective plasticizers and adjuvants include mineral oils,polybutenes, phthalates, etc. Plasticizers include phthalates such asdiisoundecyl phthalate (DIUP), diisononylphthalate (DINP),dioctylphthalates (DOP), and polybutenes.

[0092] Effective processing aids, lubricants, waxes, and oils includelow molecular weight products such as wax, oil or low Mn polymer, (lowmeaning Mn below 5000, below 4000, below 3000, or below 2500). Effectivewaxes include polar or non-polar waxes, functionalized waxes,polypropylene waxes, polyethylene waxes, and wax modifiers. Effectivefunctionalized waxes include those modified with an alcohol, an acid, ora ketone.

[0093] Some invention polymers are functionalized after polymerization.Functionalized means that the polymer has been contacted with anunsaturated acid or anhydride. Suitable unsaturated acids or anhydridesinclude any unsaturated organic compound comprising one double bond andone carbonyl group. Representative acids include carboxylic acids,anhydrides, esters and their salts, both metallic and non-metallic. Someuseful organic compound contains an ethylenic unsaturation conjugatedwith a carbonyl group (—C═O). Examples include maleic, fumaric, acrylic,methacrylic, itaconic, crotonic, alpha.methyl crotonic, and cinnamicacids as well as their anhydrides, esters and salt derivatives. Theunsaturated acid or anhydride is present at 0.1-10 wt %, alternatively0.5-7 wt % or 1-4 wt % based upon the weight of the hydrocarbon resinand the unsaturated acid or anhydride. Specific examples include waxesmodified by methyl ketone, maleic anhydride, or maleic acid. Suitablelow Mn polymers include lower α-olefins polymers such as propylene,butene, pentene, hexene, etc. Some embodiments select the polymer suchthat it includes polybutene having an Mn of less than 1000.

Applications

[0094] Invention polymers (and their blends as described above) whetherformed in situ or by physical blending are used in any knownthermoplastic or elastomer application. Examples include uses in moldedparts, films, tapes, sheets, tubing, hose, sheeting, wire and cablecoating, adhesives, shoe soles, bumpers, gaskets, bellows, films,fibers, elastic fibers, nonwoven materials, spunbond materials,sealants, surgical gowns, and medical devices.

[0095] Adhesives

[0096] Invention polymers or their blends can be used as adhesives,either alone or combined with tackifiers. Preferred tackifiers aredescribed above. The tackifier is typically present at about 1 wt % toabout 50 wt %, based upon the weight of the blend, more preferably 10 wt% to 40 wt %, even more preferably 20 wt % to 40 wt %. Other additives,as described above, may be added also.

[0097] Invention-polymer-based adhesives can be used in any adhesiveapplication, such as disposable items, packaging, laminates,pressure-sensitive adhesives, tapes labels, wood binding, paper binding,non-woven materials, road marking materials, reflective coatings, etc.In some embodiments Invention-polymer-based adhesives can be used forchassis construction in disposable diapers and napkins, elasticattachment in disposable-goods, and converting, packaging, labeling,bookbinding, woodworking, and other assembly applications. Specificarticles include diaper liquid-transfer layers, diaper leg elastics,diaper frontal tapes, diaper standing-leg cuffs, feminine-napkinadhesive strips and perishable product packaging. Specific applicationsinclude laminations for diaper outer covers, diaper elastic cuffs,filter materials, filter masks, surgical gowns, and surgical drapes;core stabilization for diapers and feminine-napkins; diaper chassisconstruction; and filtration system bonding.

[0098] The invention-polymer-based adhesives described above may beapplied to any substrate. Useful substrates include wood, paper,cardboard, plastic, thermoplastic, rubber, metal, metal foil (such asaluminum foil and tin foil), metallized surfaces, cloth, non-woven cloth(particularly polypropylene cloths), spunbonded fiber, cardboard, stone,plaster, glass (including silicon oxide (SiO_(x)) coatings applied byevaporating silicon oxide onto a film surface), foam, rock, ceramic,film, polymer foam (such as polyurethane foam), coated substrate (suchas those coated with inks, dyes, pigments), polyvinylidene chloride,etc. or their combinations. Additional useful substrates includepolyethylene, polypropylene, polyacrylates, acrylics, polyethyleneterephthalate, or any of the polymers listed above as suitable forblends. Any of the above substrates may be modified by corona treatment,electron beam irradiation, gamma irradiation, microwave, orsilanization.

[0099] Films

[0100] Invention polymers and their blends can form mono- or multi-layerfilms. These films may be formed by any of the conventional techniquesknown in the art including extrusion, co-extrusion, extrusion coating,and lamination, blowing and casting. These films may be formed by theflat film or tubular process; afterwards they may be oriented in auniaxial or in two mutually perpendicular directions in the film'splane. One or more of the layers of the film may be oriented in thetransverse or longitudinal directions to the same or different extents.This orientation may occur before or after bringing the individuallayers together. For example, a polyethylene layer can be extrusioncoated or laminated onto an oriented polypropylene layer, or thepolyethylene and polypropylene can be coextruded into a film, thenoriented. Likewise, oriented polypropylene could be laminated tooriented polyethylene or oriented polyethylene could be coated ontopolypropylene. Further orientation could follow, if desired. Filmorientation in the machine direction (MD) is typically at a ratio of1-15 or 5-7, while orientation in the transverse direction (TD) istypically at a ratio of 1-15 or 7-9. But in some embodiments, MD and TDorientation ratios are the same.

[0101] In another embodiment, the layer comprising the invention polymercompositions (or their blends) may be combined with one or more otherlayers. The other layer(s) may be any of those layers typically includedin multilayer films. For example, the other layer or layers may bepolyolefins (such as homopolymers or copolymers of C₂-C₄₀ olefins orC₂-C₂₀ olefins) or copolymers of α-olefins and other olefins (includingα-olefins and ethylene). Specific polyolefins for use as other layersinclude homopolyethylene; homopolypropylene; propylene copolymerizedwith ethylene or butene; and ethylene copolymerized with one or more ofpropylene, butene or hexene, and optional dienes. Specific examplesinclude thermoplastic polymers such as ultra-low-density polyethylene,very-low-density polyethylene, linear-low-density polyethylene,low-density polyethylene, medium-density polyethylene, high-densitypolyethylene, polypropylene, isotactic polypropylene, highly isotacticpolypropylene, syndiotactic polypropylene, random copolymer of propyleneand ethylene, butene, hexene, elastomers such as ethylene propylenerubber, ethylene propylene diene monomer rubber, neoprene, and blends ofthermoplastic polymers and elastomers, such as for example,thermoplastic elastomers and rubber toughened plastics.

[0102] Likewise, the other layer or layers may be polar polymers.Specific polar polymers include homopolymers and copolymers of esters,amides, acetates, anhydrides, copolymers of C₂-C₂₀ olefins (such asethylene and/or propylene and/or butene with one or more polar monomerssuch as acetates, anhydrides, esters, alcohol, or acrylics). Specificexamples include polyesters, polyamides, ethylene-vinyl-acetatecopolymers, and polyvinyl chloride.

[0103] Likewise, the other layer or layers may be cationic polymers.Specific cationic polymers include polymers or copolymers of geminallydisubstituted olefins, α-heteroatom-olefins, or styrenic monomers.Specific geminally disubstituted olefins include isobutylene,isopentene, isoheptene, isohexane, isooctene, isodecene, andisododecene. Specific α-heteroatom-olefins include vinyl ether and vinylcarbazole. Specific styrenic monomers include styrene, alkyl styrene,para-alkyl styrene, α-methyl styrene, chloro-styrene, andbromo-para-methyl styrene. Specific examples of cationic polymersinclude butyl rubber, isobutylene copolymerized with para methylstyrene, polystyrene, and poly-α-methyl styrene.

[0104] Finally, other specific layers can be paper, wood, cardboard,metal, metal foils (such as aluminum foil and tin foil), metallizedsurfaces, glass (including silicon oxide (SiO_(x)) coatings applied byevaporating silicon oxide onto a film surface), fabric, spunbondedfibers, and non-wovens (particularly polypropylene spun bonded fibers ornon-wovens), and substrates coated with inks, dyes, pigments,polyvinylidene chloride and the like.

[0105] The films may vary in thickness depending on the intendedapplication; films from 1-250 μm thick are usually suitable. Packagingfilms are usually from 10-60 μm thick. Sealing layers are typically0.2-50 μm. There may be a sealing layer on both the inner and outersurfaces of the film or the sealing layer may be present on only theinner or the outer surface. Additives such as antiblock additives,antioxidants, pigments, fillers, processing aids, UV stabilizers,neutralizers, lubricants, surfactants and/or nucleating agents may alsobe present in one or more layers in the films. Specific additivesinclude silicon dioxide, titanium dioxide, polydimethylsiloxane, talc,dyes, wax, calcium stearate, carbon black, low-molecular-weight resins,and glass beads. In some embodiments one or more layers may be modifiedby corona treatment, electron beam irradiation, gamma irradiation, ormicrowave. In some embodiments one or both of the surface layers ismodified by corona treatment.

[0106] The films described herein may also comprise from 5-60 wt % of ahydrocarbon resin, based upon the weight of the polymer and the resin.The resin may be combined with the polymer of the seal layer(s) or maybe combined with the polymer in the core layer(s). The resin softeningpoint is 100-200° C. or 130-180° C. Preferred hydrocarbon resins includethose described above. The films comprising a hydrocarbon resin may beoriented in uniaxial or biaxial directions to the same or differentdegrees.

[0107] The films described above may be used as stretch or cling films.Stretch-cling films are used in various bundling, packaging andpalletizing operations. A number of well-known tackifying additivesimpart cling properties to or improve the cling properties of aparticular film. Common tackifying additives include polybutenes,terpene resins, alkali metal stearates, and hydrogenated rosins androsin esters. Corona discharge can also modify film properties. Somepolymers (such as ethylene-methylacrylate copolymers) do not need clingadditives and can be used as cling layers without tackifiers.Stretch-clings films may comprise a slip layer comprising any suitablepolyolefin or combination of polyolefins such as polyethylene,polypropylene, copolymers of ethylene and propylene, and polymersobtained from ethylene or propylene copolymerized with minor amounts ofother olefins, particularly C₄-C₁₂ olefins. Polypropylene and linear lowdensity polyethylene (LLDPE) work well. Suitable polypropylene isnormally solid and isotactic (greater than 90% hot heptane insolubles)and has wide ranging melt flow rates (0.1-300 g/10 min). Additionally,the slip layer may include one or more, anti-cling (slip or antiblock)additives that may be added during polyolefin production blended inafterwards to improve the layer's slip properties. Such additives arewell-known in the art and include, for example, silicas, silicates,diatomaceous earths, talcs, and various lubricants. These additives aretypically used in amounts ranging from 100-20,000 ppm or 500-10,000 ppmby weight based upon the weight of the slip layer. The slip layer may,if desired, also include one or more other additives as described above.

[0108] Polymer products can be used for nonwovens, sealing layers,oriented polypropylene, and high-clarity thermoforming materials.

[0109] Low molecular weight varieties of high-pressure propylene homo-and co-polymers can be used for hot melt and pressure sensitiveadhesives.

[0110] Invention processes can use finely divided, supported catalyststo prepare propylene/1-hexene copolymers with greater than 1.0 mole %hex-1-ene. In addition to finely divided supports, invention processescan use fumed silica supports in which the support particle size issmall enough to form a colloid in the reaction media.

End Use Articles

[0111] Laminates comprising invention polymers can be used as athermoformable sheet where the substrate is either sprayed or injectionmolded to couple it with the ionomer/tie-layer laminate sheet. Thecomposite if formed into the desired shape to form the article, orcomposite article. Various types of substrate materials to form highlydesirable articles. The laminate can be used with plastic substratessuch as homopolymers, copolymers, foams, impact copolymers, randomcopolymers, and other applications. Specifically, some articles in whichthe present invention can be incorporated are the following: vehicleparts, especially exterior parts such as bumpers and grills, rockerpanels, fenders, doors, hoods, trim, and other parts can be made fromthe laminates, composites and methods of the invention.

[0112] Other articles can also be made, for example, counter tops,laminated surface counter tops, pool liners, pool covers, boat covers,boat sails, cable jacketing, motorcycles, snowmobiles, outdoor vehicles,marine boat hulls, canoe interiors and exteriors, luggage, clothing,fabric (combined with non-wovens), tent materials, GORETEX,Gamma-radiation resistant applications, electronic housings (TV's, VCR'sand computers), wood replacement for decks and other outdoor buildingmaterials, prefab buildings, synthetic marble panels for construction,wall coverings, hopper cars, floor coating, polymer-wood composites,vinyl tiles, bath, shower, toilet applications and translucent glassreplacement, sidings, lawn and outdoor furniture, appliances such asrefrigerators, washing machines, etc., child toys, reflective signageand other reflective articles on roads and clothing, sporting equipmentsuch as snowboards, surfboards, skis, scooters, in-line skate wheels,scratch resistant CD's, stadium seats, aerospace reentry shields,plastic paper goods, sports helmets, plastic microwaveable cookware, andother applications for coating plastics and metal where a highly glossyand scratch resistant surface is desirable, while not being subject toalgae or discoloration.

[0113] Invention copolymers are suitable for applications such as moldedarticles, including injection and blow molded bottles and molded itemsused in automotive articles, such as automotive interior and exteriortrims. Examples of other methods and applications for making thesepolymers and for which these polymers may be useful are described in theEncyclopedia of Chemical Technology, by Kirk-Othmer, Fourth Edition,vol. 17, at pages 748-819. When the application is for molded articles,the molded articles may include a variety of molded parts, particularlymolded parts related to and used in the automotive industry, such as forexample bumpers, side panels, floor mats, dashboards and instrumentpanels. Foamed articles are another application and examples wherefoamed plastics, such as foamed polypropylene, are useful may be foundin Encyclopedia of Chemical Technology, by Kirk-Othmer, Fourth Edition,vol. 11, at pages 730-783. Foamed articles are particularly useful forconstruction and automotive applications. Examples of constructionapplications include heat and sound insulation, industrial, and homeappliances, and packaging. Examples of automotive applications includeinterior and exterior automotive parts, such as bumper guards,dashboards, and interior liners.

[0114] Invention polyolefin compositions are suitable for such articlesas automotive components, wire and cable jacketing, pipes, agriculturalfilms, geomembranes, toys, sporting equipment, medical devices, castingand blowing of packaging films, extrusion of tubing, pipes and profiles,sporting equipment, outdoor furniture (e.g., garden furniture) andplayground equipment, boat and water craft components, and other sucharticles. In particular, the compositions are suitable for automotivecomponents such as bumpers, grills, trim parts, dashboards andinstrument panels, exterior door and hood components, spoiler, windscreen, hub caps, mirror housing, body panel, protective side molding,and other interior and external components associated with automobiles,trucks, boats, and other vehicles.

[0115] Other useful articles and goods may be formed economically by thepractice of this invention include crates, containers, packaging,labware, such as roller bottles for culture growth and media bottles,office floor mats, instrumentation sample holders and sample windows;liquid storage containers such as bags, pouches, and bottles for storageand IV infusion of blood or solutions; packaging material includingthose for any medical device or drugs including unit-dose or otherblister or bubble pack as well as for wrapping or containing foodpreserved by irradiation. Other useful items include medical tubing andvalves for any medical device including infusion kits, catheters, andrespiratory therapy, as well as packaging materials for medical devicesor food which is irradiated including trays, as well as stored liquid,particularly water, milk, or juice, containers including unit servingsand bulk storage containers as well as transfer means such as tubing,pipes, and such.

EXAMPLES General Preparation for the Bidentate Phenol Ligands (1 and 2)

[0116] A drop of formic acid was added to a solution of4-allyl-2,6-diisopropylaniline (5.8 mmol) and salicylaldehyde or3,5-dinitro-2-hydroxy-benzaldehyde (5.8 mmol) in alcohol (15 ml) andreaction was heated at 80° C. for 2 hrs. A yellow solid formed and wasfiltered from the solution, washed twice with cold alcohol (10 ml) andvacuum dried to yield the desired phenol ligands.

2-(2,6-diisopropyl-4-allylphenyliminomethyl)phenol (Ligand 1)

[0117] Ligand 1 was isolated as a yellow-orange solid in 97% yield. ¹HNMR (CDCl₃, 400 MHz, in ppm): δ 13.19 (s, 1H, OH), 8.30 (s, 1H, N═CH),7.42 (t, 1H, ³J(H,H)=1.6 Hz, O—Ar—Hp), 7.35 (d, 1H, 3J(H,H)=1.6 Hz,N═C—Ar—Ho), 7.06 (d, 1H, N═C—Ar—Hp), 7.00 (s, 2H, C═N—Ar—H), 6.96 (t,1H, O—Ar—Ho), 6.01 (m, 1H, 3J(H,H)=1.6 Hz, C—CH═C), 5.11 (q, 2H,3J(H,H)=1.6 Hz, C═CH2), 3.40 (d, 2H, CH2—C═C), 2.98 (m, 2H, CHMe2), 1.17(d, 12H, CH₃₁Pr).

2-(2,6-diisopropyl-4-allylphenyliminomethyl)-4,6-dinitrophenol (Ligand2)

[0118] Ligand 2 was isolated as yellow-gold crystals in 95% yield. ¹HNMR (CDCl₃, 400 MHz): δ16.27 (s, 1H, OH), 9.07 (s, 1H, N═CH), 8.50 (s,1H, Ar—H), 8.26 (s, 1H, Ar—H), 7.10 (s, 2H, C═N—Ar—H), 5.97 (m, 1H,C—CH═C), 5.16 (q, 2H, C═CH2), 3.43 (d, 2H, CH₂—C═C), 2.95 (m, 2H,CHMe₂), 1.24 (d, 12H, CH₃ iPr).

General Preparation for the Bidentate Phenol Ligands (3, 4, and 5)

[0119] A solution containing the appropriate allyl-substituted aniline(6.0 mmol), 5-methyl-3-tert-butyl-2-hydroxybenzaldehyde or3-phenyl-2-hydroxybenzaldehyde (5.8 mmol), methanol (5 ml), and formicacid (0.25 ml) was prepared and stirred at room temperature for 12 hrs.A yellow solid precipitated during this time. It was filtered, washedtwice with cold methanol (10 ml), and vacuum dried to yield the phenolligands.

2-(2,6-diisopropyl-4-allylphenyliminomethyl)-4-methyl-6-tert-butylphenol(Ligand 3)

[0120] Ligand 3 was isolated as a yellow-green oil in 92% yield. ¹H NMR(CDCl₃, 400 MHz): 613.41 (s, 1H,OH), 8.12 (s, 1H, N═CH), 7.26-6.98 (m,4H, Ar—H), 6.02 (m, 1H, C—CH═C), 5.10 (q, 2H, C═CH2), 3.39 (d, 2H,CH₂—C═C), 2.99 (m, 2H, —CHMe₂), 2.32 (s, 3H, CH₃—Ar), 1.48 (s, 9H, CH₃tBu), 1.16 (d, 12H, CH₃ iPr).

2-(2,6-diisopropyl-4-allylphenyliminomethyl)-6-phenylphenol (Ligand 4)

[0121] Ligand 4 was isolated as a yellow solid in 95% yield. ¹H NMR(CDCl₃, 400 MHz): δ 13.68 (s, 1H, OH), 8.35 (s, 1H, N═CH), 7.71-7.05 (m,8H, Ar—H), 7.00 (s, 2H, C═N—Ar—H), 6.00 (m, 1H, C—CH═C), 5.11 (q, 2H,C═CH₂), 3.39 (d, 2H, CH₂—C═C), 2.99 (m, 2H, CHMe₂), 1.16 (d, 12H, CH₃iPr).

2-(2,6-dimethyl-4-allylphenyliminomethyl)-6-phenylphenol (Ligand 5)

[0122] Ligand 5 was isolated as a yellow solid in 90% yield. ¹H NMR(CDCl₃, 400 MHz): δ13.71 (s, 1H, OH), 8.39 (s, 1H, N═CH), 7.69-7.01 (m,8H, Ar—H), 6.93 (s, 2H, C═N—Ar—H), 5.98 (m, 1H, C—CH═C), 5.09 (q, 2H,C═CH₂), 3.37 (d, 2H, CH₂—C═C), 2.19 (s, 6H, CH₃).

General Synthetic Procedure for Allyl-Substituted Phenolato Nickel (II)Complexes (6-10)

[0123] Sodium hydride (0.2 g, 8 mmol) was added to a solution of thecorresponding phenol ligand (1.5 mmol) in THF (20 ml). The mixture wasstirred at room temperature for 2 hr, centrifuged, and the clearsolution was transferred and removed under vacuum. This yielded a paleyellow solid residue. After washing with hexane (20 ml), the sodium saltof the corresponding ligand was obtained.

[0124] A benzene solution (20 ml) containing the sodium salt describedabove (1.5 mmol) and trans-[Ni(PPh₃)₂(Ph)Cl] (1.0 g, 1.44 mmol) wasstirred at room temperature. After 6 hrs, the reaction mixture wasfiltered to remove NaCl. Hexane was slowly added to the top of thefiltrate. Catalyst crystals were obtained in yields of 71-86%.

N-(salicylidene)-2′,6′-diisopropyl-4′-allylanilinato triphenylphosphinephenyl nickel (II) (6) OR2-(2,6-diisopropyl-4-allylphenyliminomethyl)phenolato triphenylphosphinephenyl nickel (II) Complex VI

[0125] Complex VI was isolated as a yellow-orange solid. Yield 0.81 g(78%). Anal. Found: C, 77.34; H, 6.44; N, 1.90; C₄₆H₄₆NNiOP requires C,76.89; H, 6.45; N, 1.95. ¹H-NMR (400 MHz, C₆D₆), δ 8.06 (d, 1H, N═CH,J(H,P)=8.4 Hz), 7.80-6.44 (m, 26H, Ar—H), 6.02 (m, 1H, C—CH═C), 5.09 (m,2H, C═CH₂), 4.17 (m, 2H, CHMe₂), 3.27 (d, 2H, CH₂—C═C, J(H,H)=6.4 Hz),1.42 (d, 6H, CH₃ iPr, J(H,H)=6.8 Hz), 1.20 (d, 6H, CH₃ iPr, J(H,H)=6.8Hz). ESI-MS: m/z 717 (M+).

N-(3,5-dinitro-salicylidene)-2′,6′-diisopropyl-4′-allylanilinatotriphenylphosphine phenyl nickel (II) (7) OR2-(2,6-diisopropyl-4-allylphenyliminomethyl)-4,6-dinitrophenolatotriphenylphosphine phenyl nickel (II) Complex VII

[0126] Complex VII was isolated as a red solid. Yield 1.05 g (90%).Anal. Found: C, 68.97; H, 5.41; N, 5.10; C₄₆H₄₄N₃NiO₅P requires C,68.33; H, 5.49; N, 5.20. ¹H-NMR (400 MHz, C₆D₆), δ 8.34 (d, 1H, N═CH,J(H,P)=2.8 Hz), 7.84-6.34 (m, 24H, Ar—H), 6.02 (m, 1H, C—CH═C), 5.12 (m,2H, C═CH₂), 3.96 (m, 2H, CHMe₂), 3.28 (d, 2H, CH₂—C═C, J(H,H)=6.0), 1.29(d, 6H, CH₃ iPr, J(H,H)=6.8 Hz), 1.12 (d, 6H, CH₃ iPr, J(H,H)=6.8 Hz).ESI-MS: m/z 807 (M+), 545 (M-PPh₃+).

N-(3-tert-butyl-5-methylsalicylidene)-2′,6′-diisopropyl-4′-allylanilinatotriphenylphosphine phenyl nickel (II) (8) OR2-(2,6-diisopropyl-4-allylphenyliminomethyl)-4-methyl-6-tert-butylphenolatotriphenylphosphine phenyl nickel (II) Complex VIII

[0127] Complex VIII was isolated as a yellow-orange solid. Yield 0.92 g(81%). Anal. Found: C, 77.90; H, 7.03; N, 1.88; C₅₁H₅₆NNiOP requires C,77.67; H, 7.16; N, 1.78. ¹H NMR (C₆D₆, 400 MHz): δ 8.10 (d, 1H, N═CH),7.90-6.34 (m, 24H, Ar—H), 6.04 (m, 1H, C—CH═C), 5.11 (q, 2H, C═CH₂),4.45 (m, 2H, CHMe₂), 3.32 (d, 2H, CH₂—C═C), 2.32 (s, 3H, CH₃—Ar), 1.36(d, 6H, CH₃ iPr), 1.26 (d, 6H, CH₃ iPr), 1.09 (s, 9H, CH₃ tBu). ESI-MS:m/z 787(M+).

N-(3-phenylsalicylidene)-2′,6′-diisopropyl-4′-allylanilinatotriphenylphosphine phenyl nickel (II) (9) OR2-(2,6-diisopropyl-4-allylphenyliminomethyl)-6-phenylphenolatotriphenylphosphine phenyl nickel (II) Complex IX

[0128] Complex IX was isolated as a yellow-orange solid. Yield 0.95 g(83%). Anal. Found: C, 78.88; H, 6.22; N, 1.73; C₅₂H₅₀NNiOP requires C,78.60; H, 6.34; N; 1.76. ¹H-NMR (400 MHz, C₆D₆), δ 8.13 (d, 1H, N═CH),7.89-6.34 (m, 30H, Ar—H), 6.02 (m, 1H, C—CH═C), 5.11 (m, 2H, C═CH₂),4.23 (m, 2H, CHMe₂), 3.32 (d, 2H, CH₂—C═C, J(H,H)=6.4), 1.35 (d, 6H, CH₃iPr, J(H,H)=6.8 Hz), 1.27 (d, 6H, CH₃ iPr, J(H,H)=6.8 Hz). ESI-MS: m/z717 (M-Ph+), 455 (M-Ph-PPh₃+).

N-(3-phenylsalicylidene)-2′,6′-dimethyl-4′-allylanilinatotriphenylphosphine phenyl nickel (II) (10) OR2-(2,6-dimethyl-4-allylphenyliminomethyl)-6-phenylphenolatotriphenylphosphine phenyl nickel (II) Complex X

[0129] Complex X was isolated as a red crystalline solid. Yield 0.95 g(86%). Anal. Found: C, 77.99; H, 5.73; N, 1.91; C₄₈H₄₂NNiOP requires C,78.07; H, 5.73; N, 1.90. ¹H-NMR (400 MHz, C₆D₆), δ 8.07 (d, 1H, N═CH,J(P,H)=8.4 Hz), 7.78-6.44 (m, 30H, H—Ar), 6.01 (m, 1H, C—CH═C), 5.10 (d,2H, C═CH₂, J(H,H)=1.6 Hz), 3.19 (d, 2H, CH₂—C═C, J(H,H)=6.4 Hz), 2.53(s, 6H, CH₃). ESI-MS: m/z 662 (M-Ph+), 400 (M-Ph-PPh₃+).

[0130] The Ni (II) complexes are single component catalysts for ethylenepolymerization or oligomerization.

Homogenous Polymerization with the Allyl-Substituted Phenolato Nickel(II) Self-Immobile Catalysts

[0131] A 500 ml autoclave was charged with 100 ml toluene under anatmosphere of argon. A solution of the allyl-substituted phenolatonickel(II) complexes (10-65 μmole) in toluene (20 ml) was added to theautoclave. After purging the autoclave three times with ethylene gas,the ethylene pressure was raised to the specified value and maintainedfor the specified time. Polymerization was terminated by adding methanoland dilute HCl (10%). The solid polyethylene was filtered, washed withmethanol, and dried at 40° C. in vacuum. TABLE 1 Ethylene PolymerizationData for Catalyst 9 (R¹ = Ph, R² = H, R³, R⁴ = iPr). Catalyst T PressureActivity^(a) Run No. μmol ° C. atm 10⁵ g PE/mol Ni · hr Mμ × 10⁻³  165.4 27 4 1.81 82.8  2 65.4 27 1 Trace  3 65.4 27 2 0.93 129.3  4 32.727 4 3.14 96.0  5 15.1 27 4 2.41 372.4  6 7.6 27 4 Trace  7 11.3 27 41.26 196.4  8 11.3 27 4 1.14 247.3  9 32.7 27 3 0.45 238.0  10^(b) 32.727 4 3.70 171.5 11 32.7 47 3 2.23 74.2 12 32.7 67 3 2.00 4.4 13 32.7 573 2.18 11.8 14 32.7 37 3 1.81 265.3 15 65.4 27 3 1.30 87.2 16 49.1 27 42.07 31.1 17 65.4 27 4 1.32

[0132] The PE produced from catalyst 9 has narrow MWD (PDI=3.1) and lowbranches (7 Me/1000 C by ¹³C NMR). DSC results indicate that the PE is alinear polymer with high crystallinity and high melting point.

[0133] While certain representative embodiments and details have beenshown to illustrate the invention, it will be apparent to skilledartisans that various process and product changes from those disclosedin this application may be made without departing from this invention'sscope, which the appended claims define.

[0134] All cited patents, test procedures, priority documents, and othercited documents are fully incorporated by reference to the extent thatthis material is consistent with this specification and for alljurisdictions in which such incorporation is permitted.

[0135] Certain features of the present invention are described in termsof a set of numerical upper limits and a set of numerical lower limits.This specification discloses all ranges formed by any combination ofthese limits. All combinations of these limits are within the scope ofthe invention unless otherwise indicated.

What is claimed is:
 1. A composition comprising the product ofcombining, in the presence of a free radical initiator, a catalystprecursor and at least one catalyst polymerization monomer wherein thecatalyst polymerization monomer is polymerizable by free-radicalpolymerization and wherein the catalyst precursor has the formula:

wherein (a) R¹ and R² are independently hydrogen, NO₂, or hydrocarbylgroups; (b) R³ and R⁴ are independently hydrogen or hydrocarbyl groups;(c) TM is a Group-4-11 metal; (d) X is an abstractable ligand; and (e) Yis a neutral Lewis base.
 2. The composition of claim 1 wherein ahydrocarbyl group is a C₁-C₅₀ hydrocarbyl group.
 3. The composition ofclaim 2 wherein a hydrocarbyl group is a C₁-C₄₀ hydrocarbyl group. 4.The composition of claim 3 wherein a hydrocarbyl group is a C₁-C₂₀hydrocarbyl group.
 5. The composition of claim 1 wherein TM is aGroup-10 transition metal.
 6. The composition of claim 1 wherein TM isselected from Ni.
 7. The composition of claim 1 wherein the abstractableligands are independently halide radicals, hydride radicals, hydrocarbylradicals, or hydrocarbyl-substituted, organometalloid radicals.
 8. Thecomposition of claim 7 wherein abstractable ligands are independentlyhalide, alkoxide, aryloxide, amide, or phosphide radicals.
 9. Thecomposition of claim 8 wherein abstractable ligands are chloride,bromide, iodide, methyl, ethyl, propyl, butyl, pentyl, hexyl, phenyl,heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl,pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl, eicosyl,heneicosyl, docosyl, tricosyl, tetracosyl, pentacosyl, hexacosyl,heptacosyl, octacosyl, nonacosyl, triacontyl, hydride, phenyl, benzyl,phenethyl, tolyl, methoxy, ethoxy, propoxy, butoxy, dimethylamino,diethylamino, methylethylamino, phenoxy, benzoxy, allyl, 1,1-dimethylallyl, 2-carboxymethyl allyl, acetylacetonate,1,1,1,5,5,5-hexa-fluoroacetylacetonate, 1,1,1-trifluoro-acetylacetonate,or 1,1,1-trifluoro-5,5-di-methylacetylacetonate radicals.
 10. Thecomposition of claim 9 wherein at least one abstractable ligand ischloride.
 11. The composition of claim 1 wherein the catalystpolymerization monomer is selected from styrene, vinyl styrene, alkylstyrene, isobutylene, isoprene, or butadiene.
 12. The composition ofclaim 11 wherein the catalyst polymerization monomer is styrene.
 13. Thecomposition of claim 1 wherein the free radical initiator is selectedfrom azo initiators or peroxides.
 14. The composition of claim 13wherein the free radical initiator is selected from dialkyldiazenes,hyponitrites, diacyl peroxides, dialkyl peroxydicarbonates, peresters,alkyl hydroperoxides, dialkyl peroxides, or inorganic peroxides.
 15. Thecomposition of claim 14 wherein the free radical initiator is selectedfrom 2,2′-azobis(2-methylpropanenitrile),1,1-azobis(1-cyclohexanenitrile), 4,4′-azobis(4-cyanovaleric acid),triphenylmethylazobenzene, di-t-butyl hyponitrite, dicumyl hyponitrite,dibenzoyl peroxide, didodecanoyl peroxide, diacetyl peroxide,diisopropyl ester, dicyclohexyl ester, cumyl hydroperoxide, t-butylhydroperoxide, dicumyl peroxide, di-t-butyl peroxide, hydrogen peroxide,and persulfate initiators.
 16. The composition of claim 1 wherein Y isselected from amines, phosphines, or nitriles.
 17. The composition ofclaim 16 wherein Y is selected from triphenyl phosphine or acetonitrile.18. An olefin polymerization method comprising contacting thecompositions of claim 1 with an olefin.
 19. The composition of claim 1wherein the catalyst precursor has the formula:

wherein (a) R¹ and R² are independently hydrogen, NO₂, or hydrocarbylgroups; (b) R³ and R⁴ are independently hydrogen or hydrocarbyl groups;(c) TM is a Group-4-11 metal; (d) X is an abstractable ligand;